CN101693181A - Silicon oxide and protamine microcapsule and preparation method thereof - Google Patents
Silicon oxide and protamine microcapsule and preparation method thereof Download PDFInfo
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- CN101693181A CN101693181A CN200910070809A CN200910070809A CN101693181A CN 101693181 A CN101693181 A CN 101693181A CN 200910070809 A CN200910070809 A CN 200910070809A CN 200910070809 A CN200910070809 A CN 200910070809A CN 101693181 A CN101693181 A CN 101693181A
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Abstract
The invention relates to a silicon oxide and protamine microcapsule and a preparation method thereof. The silicon oxide and protamine microcapsule is prepared by using a calcium carbonate particulate as a template and sodium silicate and protamine as raw materials, wherein the mass ration of the sodium silicate to the protamine is 1:1-7:1. The preparation method comprises the following steps: firstly preparing the calcium carbonate particulate with negative charges as the template; interacting the protamine with positive charges and the calcium carbonate particulate with negative charges and alternately absorbing to the template; inducing the forming of silicon oxide by using the biomineralizing function of the protamine when three to five double-layers are generated on the template; removing the inner core of the calcium carbonate by EDTA-2Na. The invention is gentle in reaction conditions during the preparation of the silicon oxide and protamine microcapsule. The prepared silicon oxide and protamine microcapsule has the advantages of gentle reaction condition, size controllability, good stability, and excellent repeatability.
Description
Technical field
The present invention relates to a kind of silica and protamine microcapsule and preparation method thereof, specifically is the preparation method that silica and protamine hydridization prepare microcapsules.
Background technology
Nowadays micro-capsule is used to fields such as the embedding protection of microreactor, pharmaceutical carrier, cell and enzyme and gene transfection more and more.Traditional microcapsule preparation method mainly contains three kinds: (1) chemical method, chemical method are meant the method that the chemical reaction encystation takes place in liquid phase.Currently used chemical method mainly contains 2 kinds, i.e. interface polycondensation and chemical radiation.Though these class methods can access the micro-capsule of size than homogeneous, its size often is difficult to regulate.(2) physical-chemical process, this law is encystation in liquid phase, promptly in the mixture of capsule core material and capsule material, add another kind of material or adopt other suitable methods that the solubility of capsule material is reduced and condense upon capsule core material around, form a cenotype and separate out, so be called phase separation method again.The equipment that is characterized in is simple, and the macromolecular material wide material sources are applicable to the microencapsulation of multiple medicine, and shortcoming is the problem of micro-capsule adhesion, gathering, and condition is difficult to control etc. in the technical process.(3) physics and Mechanical Method, these class methods mainly are the physical changes by microcapsule capsule wall material, carry out the micro-capsule preparation in conjunction with certain mechanical processing tools.The method is comparatively difficult to the control of the physicochemical properties of micro-capsule.
Adopt the micro-capsule of covalent layer-by-layer self-assembling technique preparation then to have characteristics such as high-modulus, high stability, wherein be can be to the physical and chemical performance accuracy controlling on surface for biggest advantage.At first be the regulation and control to film thickness, the regulation and control of thickness can be regulated by several aspects: the assembled material that (1) is selected; (2) Zu Zhuan the number of plies can be followed the tracks of assembling process by elliptical polarization technology or ultraviolet etc., and the thickness of film can be linear growth along with the increase of the number of plies; (3) assembling condition, under the different assembling conditions, the thickness that obtains is often different.For example the ionic strength in the solution can influence the thickness of every tunic of assembling strongly; Temperature and solvent polarity etc. are all influential to thickness.By with upper type, can be at several dusts accuracy controlling thickness in the scope of several nanometers.Next is the regulation and control to the surface chemistry performance.The material that can be used for static self assembly layer by layer is except that synthetic polyelectrolyte, other charged species can be used for constructing multilayer film as natural macromolecular (as protein and nucleic acid), virus, inorganic nano-particle (comprise receive gold, quantum dot, fullerene, CNT etc.), the big molecule of resin-like and multivalence organic ion such as dye molecule etc.
Summary of the invention
The object of the present invention is to provide a kind of silica and protamine microcapsule and preparation method thereof, is the preparation that raw material carries out micro-capsule with silica-protamine.By at interval adsorbing sodium metasilicate and protamine makes sodium metasilicate and protamine adsorb mutually by electrostatic interaction, in the assembling process under the inducing action of protamine sodium metasilicate can generate silica, thereby reach the purpose of formation by silica and protamine layer assembly micro-capsule.Preparation condition gentleness of the present invention, the preparation raw material is easy to get, and preparation is simple, and the thickness by the assembling of the different numbers of plies being regulated and control film is also than being easier to.
A kind of silica provided by the invention and protamine microcapsule are to be template with the calcium carbonate microparticle, and sodium metasilicate and protamine are raw material, are to be prepared in 1: 1～7: 1 to form processing step according to the quality proportioning of sodium metasilicate and protamine:
Contain the calcium chloride solution of kayexalate (PSS) and the calcium carbonate CaCO that sodium carbonate liquor prepared in reaction PSS mixes
3(PSS) colloidal particles; CaCO
3Compound with PSS, be expressed as: CaCO
3(PSS).
This particulate is disperseed with the dissolving of nucleoprotamine solution, and hatching is assembled into the particle of nucleoprotamine layer, and then continues to disperse with sodium silicate solution hatching; Repeat above process, at CaCO
3(PSS) microparticle surfaces alternately adsorbs the colloidal particle that nucleoprotamine and sodium metasilicate obtain nucleocapsid structure;
The colloidal particle of nucleocapsid structure and EDTA solution stirring reaction, water washing, centrifugation; Repeat above process, remove calcium carbonate and derive from silica and the nucleoprotamine micro-capsule that assembles, store standby in the water.
The step that the preparation method of a kind of silica provided by the invention and protamine microcapsule comprises:
1) configuration concentration is the calcium chloride solution of 0.2～0.5mol/l, and to wherein adding kayexalate (PSS), making its concentration is 2～3mg/l; The sodium carbonate liquor of molar concentrations such as configuration and calcium chloride, after filtering respectively, respectively get 15～25ml calcium chloride solution and isopyknic sodium carbonate liquor, under the rotating speed of 1000～1200rpm, sodium carbonate liquor is added in the calcium chloride solution, reacted 15～25 seconds, left standstill 15～25 minutes, and obtained containing the dispersion soln of carbonic acid calcium precipitate.
2) be in the centrifuge of 3000rpm centrifugal three minutes with the gained dispersion soln at rotating speed, wash with water after centrifugal, repeated centrifugation-water-washing process secondary, supernatant is removed in the back, CaCO
3(PSS) particulate.
3) configuration concentration is the sodium silicate solution of 0.02～0.04mol/l, and regulating its PH with hydrochloric acid is 7.0～8.0.
4) protamine is dissolved in the NaCl solution of 0.5mol/l, is made into the solution of 0.5～2.0mg/mL, regulating its PH with hydrochloric acid and NaOH is 6.5～7.0.
5) twice CaCO of water washing
3(PSS) particulate, particle concentration is 1%w/w, and is centrifugal, product adds the protamine solution of step 4), makes CaCO
3(PSS) disperse again, hatching 15～30min, during slight vibration centrifuge tube calcium carbonate particle is disperseed; Centrifugation repeats twice of water washing.
6) particulate joins the sodium silicate solution of step 3), particle is disperseed again, hatching 15～30min, slightly vibration during this time, be centrifugal in the centrifuge of 3000rpm at rotating speed then, repeat to wash twice, make the micro-capsule that one deck protamine, one deck silica assemble on the surface of calcium carbonate microspheres.
7) repeating step 5) and step 6) at least twice, make protamine and sodium metasilicate and adsorb at interval and form the micro-capsule that the covalency self assembly forms.The ratio in each step is 1: 1.
8) with EDTA solution and the water washing of 0.05～0.15mol/l, the 3000rpm centrifugation repeats 3-5 time, thoroughly removes calcium carbonate, gets micro-capsule after the stoning, and with water washing three times, the micro-capsule preparation so far finishes.
The invention provides a kind of silica and protamine microcapsule and preparation method thereof.At first preparation have negative electrical charge calcium carbonate microparticle as template, positively charged protamine and electronegative sodium metasilicate by electrostatic interaction, are adsorbed on the template alternately.After three to five bilayers are arranged on the template, utilize the biomineralization function of protamine to induce the formation of silica, remove the calcium carbonate kernel with disodium ethylene diamine tetraacetate at last.The present invention prepares raw material and is easy to get, and preparation is simple, by to assembling the different numbers of plies to the THICKNESS CONTROL of film also than being easier to micro-capsule controlled amount, good stability, favorable repeatability.
Description of drawings
Fig. 1: the electron scanning micrograph in the Comparative Examples 1 after one deck micro-capsule stoning of preparation.
Fig. 2: the electron micrograph in the Comparative Examples 2 after three layers of micro-capsule stoning of preparation.
Fig. 3: embodiment 2 surperficial zeta potentials and number of plies graph of a relation.
The adsorption/desorption curve and the graph of pore diameter distribution of Fig. 4: embodiment 2 micro-capsules.
The specific embodiment
Embodiment 1
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters, the sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution, in being the electromagnetic agitation machine of 1000rpm, rotating speed reacts 20s, close electromagnetic agitation and leave standstill after 15 minutes and open electromagnetic agitation, reaction solution is stirred, get 5ml and add in the centrifuge tube, get 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The sodium silicate solution of configuration 0.03mol/l, regulating its PH with hydrochloric acid is 8; The protamine solution of configuration 2mg/ml, and to wherein adding 5844mg sodium chloride and regulating between its PH to 6.5-7.0 with hydrochloric acid and NaOH.
Add the protamine solution of 5ml 2mg/ml to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Add the 5ml sodium silicate solution to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Repeating step adds protamine and adds sodium metasilicate step 3 time.The EDTA solution of configuration 0.1mol/l adds 5ml in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 3-5 time, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, with water washing three times, just can make the protamine/silica LBL micro-capsule by 3 bilayers.
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters, the sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution, in rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and left standstill 15 minutes.Electromagnetic agitation is opened in the back, and reaction solution is stirred, and gets 5ml and adds in the centrifuge tube, gets 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The sodium silicate solution of configuration 0.03mol/, regulating its PH with hydrochloric acid is 8; The protamine solution of configuration 2mg/ml, and to wherein adding 5844mg sodium chloride and regulating between its PH to 6.5-7.0 with hydrochloric acid and NaOH.
Add the protamine solution of 5ml 2mg/ml to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Add the 5ml sodium silicate solution to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Repeating step adds protamine and adds sodium metasilicate step 5 time, and the EDTA solution of configuration 0.1mol/l adds 5ml in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 4 times, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, with water washing three times, just can make 5 double-deck nucleoprotamine/silica LBL micro-capsule.
Comparative Examples one
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters, the sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution, in rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and left standstill 15 minutes.Electromagnetic agitation is opened in the back, and reaction solution is stirred, and gets 5ml and adds in the centrifuge tube, gets 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The polyelectrolyte PSS and the albumen that will have opposite charges are dissolved in respectively in the 0.5MNaCl solution, respectively are made into the solution of 2mg/mL, and regulating pH is about 7.0.
Get certain amount of CaCO
3(PSS) particulate places centrifuge tube (particle concentration is about 1%w/w), washes twice with water, and the centrifugal 3min of each washing back 3000rpm is to remove supernatant.In centrifuge tube, add the as above protamine solution of preparation, make CaCO
3(PSS) disperse again, hatching 15min, during slight vibration centrifuge tube calcium carbonate particle is disperseed; The centrifugal supernatant that goes adds the water washing calcium carbonate particle, repeats twice.Add PSS solution then in the particle that is assembled with one deck protamine, particle disperseed again, hatching 15min, during slightly vibration, the centrifugal then supernatant that goes is washed twice.
Repeat above process, at CaCO
3(PSS) microparticle surfaces alternately adsorbs protamine and PSS, assembles the colloidal particle that obtains nucleocapsid structure behind 5 bilayers.The EDTA stoning that adds 0.02M in the colloidal particle of above nucleocapsid structure, reaction 30min, the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 4 times, thoroughly to remove calcium carbonate, just can make 5 double-deck protamine/PSS LBL micro-capsule.
Comparative Examples two
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters, the sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution, in rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and left standstill 15 minutes.Electromagnetic agitation is opened in the back, and reaction solution is stirred, and gets 5ml and adds in the centrifuge tube, gets 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The sodium silicate solution of preparation 0.03mol/, regulating its PH with hydrochloric acid is 8; The nucleoprotamine solution of configuration 2mg/ml, and to wherein adding 5844mg sodium chloride and regulating between its PH to 6.5-7.0 with hydrochloric acid and NaOH.
Add the protamine solution of 5ml 2mg/ml to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Add the 5ml sodium silicate solution to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
The EDTA solution of preparation 0.1mol/l adds 5ml in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 4 times, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, with water washing three times, just can make 1 double-deck protamine/sodium metasilicate LBL micro-capsule.
Claims (2)
1. silica and protamine microcapsule is characterized in that it is is template with the calcium carbonate microparticle, and sodium metasilicate and protamine are raw material, according to the quality proportioning of sodium metasilicate and protamine for (1: 1-7: 1) be prepared and form concrete processing step:
Contain the calcium chloride solution of kayexalate (PSS) and the calcium carbonate CaCO that sodium carbonate liquor prepared in reaction PSS mixes
3(PSS) colloidal particles;
This particulate is disperseed with the dissolving of nucleoprotamine solution, and hatching is assembled into the particle of nucleoprotamine layer, and then continues to disperse with sodium silicate solution hatching; Repeat above process, at CaCO
3(PSS) microparticle surfaces alternately adsorbs the colloidal particle that nucleoprotamine and sodium metasilicate obtain nucleocapsid structure;
The colloidal particle of nucleocapsid structure and EDTA solution stirring reaction, water washing, centrifugation; Repeat above process, remove calcium carbonate and derive from silica and the nucleoprotamine micro-capsule that assembles, store standby in the water.
2. the preparation method of silica and protamine microcapsule is characterized in that the step that comprises:
1) configuration concentration is the calcium chloride solution of 0.2～0.5mol/l, and to wherein adding kayexalate, making its concentration is 2～3mg/l; The sodium carbonate liquor of molar concentrations such as configuration and calcium chloride, after filtering respectively, respectively get 15～25ml calcium chloride solution and isopyknic sodium carbonate liquor, under the rotating speed of 1000～1200rpm, sodium carbonate liquor is added in the calcium chloride solution, reacted 15～25 seconds, left standstill 15～25 minutes, and obtained containing the dispersion soln of carbonic acid calcium precipitate;
2) be in the centrifuge of 3000rpm centrifugal three minutes with the gained dispersion soln at rotating speed, wash with water after centrifugal, repeated centrifugation-water-washing process secondary, supernatant is removed in the back, CaCO
3(PSS) particulate;
3) configuration concentration is the sodium silicate solution of 0.02～0.04mol/l, and regulating its PH with hydrochloric acid is 7.0～8.0;
4) protamine is dissolved in the NaCl solution of 0.5mol/l, is made into the solution of 0.5～2.0mg/mL, regulating its PH with hydrochloric acid and NaOH is 6.5～7.0;
5) twice CaCO of water washing
3(PSS) particulate, particle concentration is 1%w/w, and is centrifugal, product adds the protamine solution of step 4), makes CaCO
3(PSS) disperse again, hatching 15～30min, during slight vibration centrifuge tube calcium carbonate particle is disperseed; Centrifugation repeats twice of water washing;
6) particulate joins the sodium silicate solution of step 3), particle is disperseed again, hatching 15～30min, slightly vibration during this time, be centrifugal in the centrifuge of 3000rpm at rotating speed then, repeat to wash twice, make the micro-capsule that one deck protamine, one deck silica assemble on the surface of calcium carbonate microspheres;
7) repeating step 5) and step 6) at least twice, make protamine and sodium metasilicate and adsorb at interval and form the micro-capsule that the covalency self assembly forms; The ratio in each step is 1: 1;
8) with EDTA solution and the water washing of 0.05～0.15mol/l, the 3000rpm centrifugation repeats 3-5 time, thoroughly removes calcium carbonate, gets micro-capsule after the stoning, and with water washing three times, the micro-capsule preparation so far finishes.
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